EP1753891B1 - Msvd coating process - Google Patents
Msvd coating process Download PDFInfo
- Publication number
- EP1753891B1 EP1753891B1 EP05795589.0A EP05795589A EP1753891B1 EP 1753891 B1 EP1753891 B1 EP 1753891B1 EP 05795589 A EP05795589 A EP 05795589A EP 1753891 B1 EP1753891 B1 EP 1753891B1
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- European Patent Office
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- metal
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- 238000000576 coating method Methods 0.000 title claims description 38
- 239000000758 substrate Substances 0.000 claims description 62
- 229910052751 metal Inorganic materials 0.000 claims description 52
- 239000002184 metal Substances 0.000 claims description 52
- 239000007789 gas Substances 0.000 claims description 37
- 238000000034 method Methods 0.000 claims description 34
- 230000007704 transition Effects 0.000 claims description 32
- 239000011248 coating agent Substances 0.000 claims description 28
- 229910052782 aluminium Inorganic materials 0.000 claims description 27
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 27
- 239000010703 silicon Substances 0.000 claims description 25
- 229910052710 silicon Inorganic materials 0.000 claims description 25
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 23
- 239000010936 titanium Substances 0.000 claims description 23
- 229910052719 titanium Inorganic materials 0.000 claims description 23
- 229910052709 silver Inorganic materials 0.000 claims description 19
- 239000004332 silver Substances 0.000 claims description 19
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 16
- 239000000203 mixture Substances 0.000 claims description 16
- 239000011521 glass Substances 0.000 claims description 15
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 14
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 13
- 239000001301 oxygen Substances 0.000 claims description 13
- 229910052760 oxygen Inorganic materials 0.000 claims description 13
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 7
- 239000000377 silicon dioxide Substances 0.000 claims description 7
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 6
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 6
- 239000000956 alloy Substances 0.000 claims description 6
- 229910045601 alloy Inorganic materials 0.000 claims description 6
- 229910052802 copper Inorganic materials 0.000 claims description 6
- 239000010949 copper Substances 0.000 claims description 6
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical group [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 6
- 229910052737 gold Inorganic materials 0.000 claims description 6
- 239000010931 gold Substances 0.000 claims description 6
- 229910052735 hafnium Inorganic materials 0.000 claims description 6
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 claims description 6
- 229910052727 yttrium Inorganic materials 0.000 claims description 6
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 claims description 6
- 229910052726 zirconium Inorganic materials 0.000 claims description 6
- 238000005086 pumping Methods 0.000 claims description 5
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 239000011701 zinc Substances 0.000 claims description 4
- 229910052725 zinc Inorganic materials 0.000 claims description 4
- 239000010410 layer Substances 0.000 description 43
- 238000000151 deposition Methods 0.000 description 19
- 230000008021 deposition Effects 0.000 description 17
- 239000011247 coating layer Substances 0.000 description 15
- 239000000463 material Substances 0.000 description 12
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 10
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 6
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 6
- 239000011261 inert gas Substances 0.000 description 6
- 229910052786 argon Inorganic materials 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 238000004544 sputter deposition Methods 0.000 description 5
- 239000013077 target material Substances 0.000 description 5
- 230000005540 biological transmission Effects 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 3
- 230000005855 radiation Effects 0.000 description 3
- 239000011787 zinc oxide Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000000740 bleeding effect Effects 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 239000008199 coating composition Substances 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012544 monitoring process Methods 0.000 description 2
- 229910052718 tin Inorganic materials 0.000 description 2
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 2
- 229920006384 Airco Polymers 0.000 description 1
- 229910001335 Galvanized steel Inorganic materials 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 238000006124 Pilkington process Methods 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 239000011358 absorbing material Substances 0.000 description 1
- 230000001464 adherent effect Effects 0.000 description 1
- 239000005347 annealed glass Substances 0.000 description 1
- 239000005388 borosilicate glass Substances 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 description 1
- 238000005137 deposition process Methods 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000005357 flat glass Substances 0.000 description 1
- 239000005329 float glass Substances 0.000 description 1
- 239000008397 galvanized steel Substances 0.000 description 1
- 239000005346 heat strengthened glass Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000000752 ionisation method Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 229910000108 silver(I,III) oxide Inorganic materials 0.000 description 1
- 239000005361 soda-lime glass Substances 0.000 description 1
- 238000005118 spray pyrolysis Methods 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 238000001771 vacuum deposition Methods 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
- C03C17/36—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal
- C03C17/3602—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer
- C03C17/3605—Coatings of the type glass/metal/inorganic compound
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
- C03C17/3411—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions with at least two coatings of inorganic materials
- C03C17/3429—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions with at least two coatings of inorganic materials at least one of the coatings being a non-oxide coating
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
- C03C17/36—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
- C03C17/36—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal
- C03C17/3602—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer
- C03C17/3644—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer the metal being silver
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
- C03C17/36—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal
- C03C17/3602—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer
- C03C17/3649—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer made of metals other than silver
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
- C03C17/36—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal
- C03C17/3602—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer
- C03C17/3689—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer one oxide layer being obtained by oxidation of a metallic layer
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
- C03C17/36—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal
- C03C17/3602—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer
- C03C17/3694—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer one layer having a composition gradient through its thickness
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/0021—Reactive sputtering or evaporation
- C23C14/0036—Reactive sputtering
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/34—Sputtering
- C23C14/35—Sputtering by application of a magnetic field, e.g. magnetron sputtering
- C23C14/352—Sputtering by application of a magnetic field, e.g. magnetron sputtering using more than one target
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2218/00—Methods for coating glass
- C03C2218/10—Deposition methods
- C03C2218/15—Deposition methods from the vapour phase
- C03C2218/154—Deposition methods from the vapour phase by sputtering
- C03C2218/156—Deposition methods from the vapour phase by sputtering by magnetron sputtering
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2218/00—Methods for coating glass
- C03C2218/30—Aspects of methods for coating glass not covered above
- C03C2218/32—After-treatment
- C03C2218/322—Oxidation
Definitions
- the present invention relates to methods for coating substrates; especially magnetron vacuum sputtering deposition methods.
- Glass substrates are used in a variety of applications including architectural applications, automotive applications, consumer appliances, etc. Oftentimes, the glass is coated with a functional coating(s) to provide the required properties. Examples of functional coatings include solar control coatings, conductive coatings, photocatalytic coatings, low emissivity I coatings, etc.
- MSVD magnetron sputtered vacuum deposition
- MSVD processes are performed in coaters having one or more coating zones.
- a typical MSVD coater has between four and twenty zones.
- Each zone includes one or more targets, usually three, for depositing a specific type of material on a substrate.
- Each target is placed in a bay which has its own gas feeds by which gas comes into the zone. Although gas comes into a zone in different places, all of the gas that comes into the zone leaves at a certain place in the zone.
- Each zone in a coater is run, i.e. operated to deposit a coating layer, in one of three modes- metal mode, transition mode, or oxide mode.
- the amount of reactive gas e.g. a gas like hydrogen or nitrogen that is capable of reacting with a target in the zone, determines the mode.
- the gaseous atmosphere in the zone consists of only non-reactive gas, e.g. argon, and the zone is run to deposit a layer of metal on a substrate.
- metal mode generally has the fastest deposition rate, with the exception of a few target materials such as tungsten.
- transition mode the gaseous atmosphere in the zone consists of both non-reactive gas and a reactive gas, and the zone is run to deposit a layer of oxide on the substrate.
- the concentration of the reactive gas is constantly monitored and adjusted to ensure the oxide layer is being deposited at the maximum rate.
- the deposition rate in transition mode is slower than the deposition rate of metal mode but faster than the deposition rate of oxide mode.
- oxide mode the gaseous atmosphere in the zone consists of both non-reactive gas and reactive gas, and the zone is run to deposit a layer of oxide on the substrate. Of the three modes, oxide mode has the slowest deposition rate.
- the deposition rate in metal mode can be up to ten times faster than the deposition rate in oxide mode.
- each bay in a single zone in an MSVD coater is run in the same mode; either metal mode, transition mode, or oxide mode. If different bays in a zone were run in different modes, oxide mode and metal mode, for example, reactive gas entering the bay being run in oxide mode could leak over (also referred to as "bleed through") into the bay being run in metal mode and negatively impact the deposition process. The desired metal layer would not be deposited and/or the speed of the deposition would be reduced.
- the types of coating compositions that can be deposited and the efficiency at which they can be deposited are limited by the total number of zones in the coater.
- a coating that has three silver layers sandwiched by four zinc oxide layers cannot be deposited via a continuous process in a coater having less than seven zones.
- Four zones are required to run in either oxide mode or transition mode to deposit the layers of zinc oxide and three zones are required to run in metal mode to deposit the silver layers.
- Coaters can be expanded to include more coating zones. Some multi-zone coaters are designed to accommodate an expansion to include more zones, but others are not. Regardless, it is expensive to add more zones to an existing coater. Typically, it will cost between $1 and $5 million to add one zone to an existing coater, depending on whether the coater was designed for expansion or not.
- the present invention provides a method for coating a substrate that includes running a single zone of a MSVD multi-zone coater in at least two different modes, thereby reducing the total number of zones required to apply a given coating.
- a substrate is coated in a single zone of a MSVD coater wherein the zone includes at least two bays, comprising: running a first bay of a zone including a first target in metal mode to deposit a metal layer on the substrate, wherein the first target is selected from gold, copper, silver, titanium, zirconium, hafnium, yttrium and mixtures and alloys thereof; and running a second bay of a zone including a second target in transition or oxide mode to deposit an oxide layer on the substrate, wherein the second target is selected from titanium, silicon, zinc, aluminum, and combinations thereof, and wherein running the second bay includes pumping oxygen as a reactive gas into the zone.
- the present invention is a method of coating a substrate in a single zone of a MSVD coater wherein the zone includes at least two bays, comprising running a first bay of a zone including a first target in metal mode and running a second bay of a zone including a second target in transition or oxide mode, wherein the ⁇ G of formation of the target being run in transition mode or oxide mode is equal to or less than -160 kcal/mole O 2 or the difference in ⁇ G between the target being run in transition mode or oxide mode and the target being run in metal mode is at least 60 kcal/mole O 2 .
- a stated range of "1 to 10" should be considered to include any and all subranges between (and inclusive of) the minimum value of 1 and the maximum value of 10; that is, all subranges beginning with a minimum value of 1 or more and ending with a maximum value of 10 or less, e.g., 1.0 to 3.8, 6.6 to 9.7 and 5.5 to 10.
- the terms “applied on/over”, “formed on/over”, “deposited on/over”, or “provided on/over” mean formed, deposited, overlay or provided on but not necessarily in contact with the surface.
- a coating layer "formed over" a substrate does not preclude the presence of one or more other coating layers or films of the same or different composition located between the formed coating layer and the substrate.
- the substrate can include a conventional coating such as those known in the art for coating substrates, such as glass or ceramic.
- running a coater refers to the operation of a coater in a manner that results in a coating layer(s) being deposited on a substrate.
- the method of the present invention comprises running a single zone of an MSVD coater in at least two different modes to deposit a layer(s) of coating on a substrate.
- the present invention therefore defines a method of coating a substrate in a single zone of a MSVD coater wherein the zone includes at least two bays, comprising: running a first bay of a zone including a first target in metal mode to deposit a metal layer on the substrate, wherein the first target is selected from gold, copper, silver, titanium, zirconium, hafnium, yttrium and mixtures and alloys thereof; and running a second bay of a zone including a second target in transition or oxide mode to deposit an oxide layer on the substrate, wherein the second target is selected from titanium, silicon, zinc, aluminum, and combinations thereof, and wherein running the second bay includes pumping oxygen as a reactive gas into the zone.
- the zone is a vacuum chamber equipped with various pumps to evacuate the chamber and to introduce one or more gases into the chamber as is well known in the art.
- the zone is isolated from other zones in the MSVD coater by narrow tunnels and/or pumps.
- the zone contains at least two targets, generally three. Each target is housed in a bay which has its own gas feed. Although the targets have separate gas feeds, all of the gas fed into the zone is pumped out from one location.
- the targets utilized in the present invention are typical targets as are well known in the art for an MSVD process.
- a non-limiting example of a suitable target is a rotary target commercially available from AIRCO Coating Technology under the trademark "C-MAG".
- suitable targets include those made of gold, copper, silver, zirconium, hafnium, aluminum, and yttrium as well as combinations of the aforementioned metals and alloys thereof.
- the previously mentioned targets are generally used to sputter deposit as a metal layer; hence, they are generally sputtered in metal mode.
- Other non-limiting examples of suitable targets include those made of titanium, silicon, tin, zinc, aluminum, combinations thereof, etc.
- the previously mentioned targets are generally used to sputter deposit as an oxide layer; hence, they are generally sputtered in either transition mode or oxide mode.
- a target can comprise from 5 weight percent to 95 weight percent aluminum and 5 weight percent to 95 weight percent silicon, for example, 10 weight percent to 90 weight percent aluminum and 90 weight percent to 10 weight percent silicon, or 15 weight percent to 90 weight percent aluminum and 85 weight percent to 10 weight percent silicon, or 50 weight percent to 75 weight percent aluminum and 50 weight percent to 25 weight percent silicon.
- the target can comprise 60 weight percent silicon and 40 weight percent aluminum; or 25 weight percent silicon and 75 weight percent aluminum; or 90 weight percent silicon and 10 weight percent aluminum.
- the targets in the zone need to be chosen effectively to carry out the present invention. More particularly, the targets that can be placed in a single zone to carry out the present invention depend on the coating to be deposited, the Gibbs Free Energy of formation ( ⁇ G) of the target oxides in the zone, and the deposition rates of the respective targets. ⁇ G is energy which is, or which can be, available to do useful work.
- the ⁇ G of the target(s) oxides being run in transition mode or oxide mode is equal to or less than -160 kcal/mole O 2 , for example -165 kcal/mole O 2 .
- the target absorbs all of the reactive gas and there is none left to bleed through to other targets in the zone.
- Numerical values for the ⁇ G for many oxides can be found in Free Energy of Formation of Binary Compound, by Thomas Reed, MIT Press, ISBN 0 262 18051 0.
- the difference in ⁇ G between the target(s) being run in transition mode or oxide mode and the target(s) being run in metal mode should be at least 60 kcal/mole O 2 , for example, at least 75 kcal/mole O 2 , or at least 100 kcal/mole O 2 .
- the bigger difference in ⁇ G between the target(s) being run in transition mode or oxide mode and the target(s) being run in metal mode the better the invention will operate because the chances of any bleed through is minimized.
- the closer the ⁇ G of the target(s) being run in transition mode or oxide mode is to zero the more bleed through is likely to occur because the target's affinity to react with reactive gas in its bay is not as high.
- the amount of bleed through (and hence the difference in ⁇ G between the target(s) being run in transition mode or oxide mode and the target(s) being run in metal mode) is not as important as it is in others.
- the required difference in ⁇ G between the target(s) being run in transition mode or oxide mode and the target(s) being run in metal mode depends on the coating layers that are being deposited. For example, if a bay including a titanium target is being sputtered in metal mode to deposit a layer of titanium, but the layer of titanium is being deposited to eventually convert to titania, the bleed through from a bay being run in oxide mode or metal mode is less critical to the formed coating configuration. The titanium is being deposited so that it may be oxidized during subsequent processing.
- the deposition rate of a particular target can be adjusted to account for a given amount of bleed through. For example, if a bay being run in transition mode or oxide mode is bleeding through oxygen, the deposition rate of the target can be slowed by reducing the power to the target. By reducing the deposition rate of the target, the reactions between the target and the reactive gas can be increased. The more reactions occurring between the reactive gas and the target, the less bleed through from the bay.
- the method of the present invention can be used on various substrates.
- suitable substrates include, but are not limited to, metal substrates, such as but not limited to steel, galvanized steel, stainless steel, and aluminum; ceramic substrates; tile substrates; glass substrates; or mixtures or combinations of any of the above.
- the substrate can be conventional untinted soda-lime-silica-glass, i.e., "clear glass", or can be tinted or otherwise colored glass, borosilicate glass, leaded glass, tempered, untempered, annealed, or heat-strengthened glass.
- the glass can be of any type, such as conventional float glass or flat glass, and can be of any composition having any optical properties, e.g., any value of visible radiation transmission, ultraviolet radiation transmission, infrared radiation transmission, and/or total solar energy transmission.
- Types of glass suitable for the practice of the invention are described, for example but not to be considered as limiting, in U.S. Patent Nos. 4,746,347 ; 4,792,536 ; 5,240,886 ; 5,385,872 ; and 5,393,593 .
- the substrate can be any thickness. Generally, the substrate is thicker for architectural applications than for automotive applications.
- the substrate can be glass having a thickness ranging from 1 mm to 20 mm, for example, 1 mm to 10 mm, or 2 mm to 6 mm.
- the substrate can be at least one glass ply in a laminated automotive windshield or sidelight.
- the glass typically is up to 5.0 mm thick, for example, up to 3.0 mm thick, or up to 2.5 mm thick, or up to 2.1 mm thick.
- the glass substrate can be manufactured using conventional float processes, e.g., as described in U.S. Patent Nos. 3,083,551 ; 3,220,816 ; and 3,843,346 .
- the proper gaseous atmosphere is created in each zone by continuously pumping one or more inert gases and/or one or more reactive gases into the bays in the zone and pumping the gas out at one location in the zone.
- the proper gaseous atmosphere depends on the composition of the coating layer(s) that is being deposited.
- the molecules of the reactive gas in the bay react with the sputtered atoms of the target material as they travel through the plasma cloud and impinge on the substrate.
- the end result is a deposited layer comprising a reacted compound, e.g., an oxide or a nitride of a metal, on the substrate.
- the plasma cloud impinges on the target material to cause a metal layer to be deposited on the substrate.
- the coating compositions produced via MSVD processes are uniform, very adherent and resistant to abrasion, peeling and cracking.
- a portion of the substrate is only exposed to one target at a time. This embodiment allows discreet layers of coating to be deposited from a single target.
- a portion of the substrate is exposed to more than one target of different materials at a given time.
- This embodiment enables a layer of coating to be deposited that is a mixture of materials from more than one target (e.g., a gradient coating layer).
- a gradient layer comprised of two materials, a first material and a second material, as described below can be formed.
- the gradient layer can be deposited in such a manner that the concentration of the first material is greatest near the bottom of the coating layer and the concentration of the second material changes, e.g., gradually increases, as the distance from the bottom of the coating layer increases.
- the region of coating furthest from the bottom of the coating layer has the greatest concentration of the second material.
- a substrate coated according to the present invention can receive additional layer of coating and can be heated.
- the coated substrate is heated, for example, to oxidize or further oxidize a metal within the coating stack.
- Additional layers such as a heat absorbing material like carbon can be applied on the coated substrate.
- a coating layer is beneficial if the coated substrate will need to be heated rapidly. Because all of the carbon can be consumed during the heating process, a final coated substrate can be made that does not include the carbon layer.
- a zone in a MSVD multi-zone coater has at least one bay run in metal mode and at least one bay run in either transition mode or oxide mode.
- the bay that will be run in metal mode comprises a target comprising silver as is well known in the art.
- a gaseous stream comprised of an inert gas, like argon, is fed into the bay containing the silver target.
- the silver target is sputtered to deposit a layer of silver on the substrate.
- the sputtering is carried out using conventional power levels and under standard conditions as is well known in the art.
- the bay that will be run in either transition mode or oxide mode comprises a target comprising a mixture of aluminum and silicon as is well known in the art.
- Two gaseous streams are fed into the bay containing the aluminum/silicon target.
- One stream comprises an inert gas, like argon, and the other stream comprises a reactive gas, like oxygen.
- the aluminum/silicon target is sputtered to deposit a layer of a mixture of alumina and silica on the silver layer.
- the amount of reactive gas in the bay being run in transition mode or oxide mode is established such that the reactive gas does not bleed through to the bay being run in metal mode.
- the gaseous environment in the bay is maintained to have very low levels of oxygen to keep the deposition rate of the target as high as possible.
- the minimum amount of oxygen necessary to deposit the target of aluminum and silicon as an oxide is fed into the bay.
- the amount of oxygen in the bay is adjusted every few milliseconds by means of a feedback system like a plasma emission monitoring (PEM) which is well known in the art.
- PEM plasma emission monitoring
- the amount of reactive gas in the bay is very important for several reasons. If too much reactive gas is present in a bay, reactions occur on the target surface (referred to as "target poisoning" in the art) and not in the sputtered plasma, causing the deposition rate to decrease from a transition mode rate to an oxide mode rate. If too little reactive gas is present in the bay, a sub-stoichiometric compound, such as a sub-oxide, and not the desired compound will be deposited on the substrate.
- the thickness of the deposited silver layer can range from 50 ⁇ to 300 ⁇ , for example, from 60 ⁇ to 200 ⁇ , or from 70 ⁇ to 150 ⁇ .
- the thickness of the deposited alumina/silica layer can range from 40 ⁇ to 400 ⁇ , for example, 100 ⁇ to 350 ⁇ , or 150 ⁇ to 250 ⁇ .
- a bay containing a target comprising a second metal that is different from the other metal in the zone, i.e. silver in this embodiment, can be located in a third bay between the two bays discussed above.
- Suitable second metals for the target include gold, copper, silver, titanium, zirconium, hafnium, yttrium and mixtures and alloys thereof.
- a target comprising titanium as is well known in the art is located in a bay between the silver target and the aluminum/silicon target in the non-limiting embodiment discussed above.
- the titanium target can be used to react with any reactive gas bleeding through from the bay being run in transition mode or oxide mode comprising aluminum and silicon so that no reactive gas reaches the bay housing the metal being run in metal mode.
- At least one bay in a zone is run in oxide mode and another bay in the zone is run in transition mode.
- the bay that will be run in oxide mode contains a target comprising a mixture of aluminum and silicon as is well known in the art.
- Two gaseous streams are fed into the bay.
- One stream comprises an inert gas, like argon, and the other stream comprises a reactive gas, like oxygen.
- the aluminum/silicon target is sputtered to deposit a layer of alumina/silica on the substrate. The sputtering is carried out using conventional power levels and under standard conditions as is well known in the art.
- the bay that will be run in transition mode contains a target comprising titanium as is well known in the art.
- Two gaseous streams are fed into the bay containing the titanium target.
- One stream comprises an inert gas, like argon, and the other stream comprises a reactive gas like, oxygen.
- the titanium target is sputtered to deposit a titanium-containing layer on the layer of alumina/silica.
- the gaseous environment in the bay is maintained to have very low levels of oxygen to keep the deposition rate of the target as high as possible.
- the minimum amount of oxygen necessary to deposit the target as an oxide is fed into the bay.
- the amount of oxygen in the bay is adjusted every few milliseconds by means of a feedback system like a plasma emission monitoring (PEM) which is well known in the art.
- PEM plasma emission monitoring
- the thickness of the deposited alumina/silica layer can range from 40 ⁇ to 400 ⁇ , for example, from 100 ⁇ to 350 A, or from 150 ⁇ to 250 ⁇ .
- the thickness of the deposited titanium-containing layer can range from 10 ⁇ to 150 ⁇ , for example, 20 ⁇ to 110 ⁇ , or 60 ⁇ to 90 ⁇ .
- One of the unique aspects of the described embodiment is that it sputters a material that isn't an oxide at the time of deposition but can be converted to an oxide by heating or other means. Specifically, the deposited titanium can be converted to titania by heating.
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Description
- The present invention relates to methods for coating substrates; especially magnetron vacuum sputtering deposition methods.
- Glass substrates are used in a variety of applications including architectural applications, automotive applications, consumer appliances, etc. Oftentimes, the glass is coated with a functional coating(s) to provide the required properties. Examples of functional coatings include solar control coatings, conductive coatings, photocatalytic coatings, low emissivity I coatings, etc.
- Today, scientists and engineers are devising increasingly complex functional coatings. More specifically, functional coatings are being designed with more discrete coating layers. Generally, the more discrete layers of coating in a multi-layer coating stack, the easier it is to control properties of the coated substrate such as color and solar properties, e.g., emissivity.
- Several techniques, such as chemical vapor deposition ("CVD"), spray pyrolysis, and magnetron sputtered vacuum deposition ("MSVD") are known in the art for applying functional coatings on a substrate. MSVD processes are best suited for complex coatings containing one or more coating layers because they allow for a wider selection of coating materials to be deposited at thinner thicknesses on a broader variety of substrates.
- MSVD processes are performed in coaters having one or more coating zones. A typical MSVD coater has between four and twenty zones. Each zone includes one or more targets, usually three, for depositing a specific type of material on a substrate. Each target is placed in a bay which has its own gas feeds by which gas comes into the zone. Although gas comes into a zone in different places, all of the gas that comes into the zone leaves at a certain place in the zone.
- Each zone in a coater is run, i.e. operated to deposit a coating layer, in one of three modes- metal mode, transition mode, or oxide mode. Generally speaking, the amount of reactive gas, e.g. a gas like hydrogen or nitrogen that is capable of reacting with a target in the zone, determines the mode. In metal mode, the gaseous atmosphere in the zone consists of only non-reactive gas, e.g. argon, and the zone is run to deposit a layer of metal on a substrate. Of the three modes, metal mode generally has the fastest deposition rate, with the exception of a few target materials such as tungsten. In transition mode, the gaseous atmosphere in the zone consists of both non-reactive gas and a reactive gas, and the zone is run to deposit a layer of oxide on the substrate. The concentration of the reactive gas is constantly monitored and adjusted to ensure the oxide layer is being deposited at the maximum rate. The deposition rate in transition mode is slower than the deposition rate of metal mode but faster than the deposition rate of oxide mode. In oxide mode, the gaseous atmosphere in the zone consists of both non-reactive gas and reactive gas, and the zone is run to deposit a layer of oxide on the substrate. Of the three modes, oxide mode has the slowest deposition rate. The deposition rate in metal mode can be up to ten times faster than the deposition rate in oxide mode.
- Conventionally, each bay in a single zone in an MSVD coater is run in the same mode; either metal mode, transition mode, or oxide mode. If different bays in a zone were run in different modes, oxide mode and metal mode, for example, reactive gas entering the bay being run in oxide mode could leak over (also referred to as "bleed through") into the bay being run in metal mode and negatively impact the deposition process. The desired metal layer would not be deposited and/or the speed of the deposition would be reduced.
- Because a single zone is always run in one mode, the types of coating compositions that can be deposited and the efficiency at which they can be deposited (the faster the rate of deposition, the faster the rate of production) are limited by the total number of zones in the coater. For example, a coating that has three silver layers sandwiched by four zinc oxide layers cannot be deposited via a continuous process in a coater having less than seven zones. Four zones are required to run in either oxide mode or transition mode to deposit the layers of zinc oxide and three zones are required to run in metal mode to deposit the silver layers. Although it may be possible to produce the described coating in a coater have less than seven zones by running the substrate through the coater more than once, such is undesirable for several reasons, chief among them, efficiency.
- Coaters can be expanded to include more coating zones. Some multi-zone coaters are designed to accommodate an expansion to include more zones, but others are not. Regardless, it is expensive to add more zones to an existing coater. Typically, it will cost between $1 and $5 million to add one zone to an existing coater, depending on whether the coater was designed for expansion or not.
- It would be extremely beneficial to have a method for coating substrates in a MSVD multi-zone coater that reduces the total number of zones required to deposit a coating. The present invention provides a method for coating a substrate that includes running a single zone of a MSVD multi-zone coater in at least two different modes, thereby reducing the total number of zones required to apply a given coating.
- In the method of the invention a substrate is coated in a single zone of a MSVD coater wherein the zone includes at least two bays, comprising: running a first bay of a zone including a first target in metal mode to deposit a metal layer on the substrate, wherein the first target is selected from gold, copper, silver, titanium, zirconium, hafnium, yttrium and mixtures and alloys thereof; and running a second bay of a zone including a second target in transition or oxide mode to deposit an oxide layer on the substrate, wherein the second target is selected from titanium, silicon, zinc, aluminum, and combinations thereof, and wherein running the second bay includes pumping oxygen as a reactive gas into the zone. Furthermore in a non-limiting embodiment, the present invention is a method of coating a substrate in a single zone of a MSVD coater wherein the zone includes at least two bays, comprising running a first bay of a zone including a first target in metal mode and running a second bay of a zone including a second target in transition or oxide mode, wherein the ΔG of formation of the target being run in transition mode or oxide mode is equal to or less than -160 kcal/mole O2 or the difference in ΔG between the target being run in transition mode or oxide mode and the target being run in metal mode is at least 60 kcal/mole O2.
- Further embodiments of the invention are defined in the appended claims.
- As used herein, spatial or directional terms, such as "left", "right", "inner", "outer", "above", "below", "top", "bottom", and the like, relate to the invention as it is shown in the drawing figures. However, it is to be understood that the invention may assume various alternative orientations and, accordingly, such terms are not to be considered as limiting.
- Further, as used herein, all numbers expressing dimensions, physical characteristics, processing parameters, quantities of ingredients, reaction conditions, and the like, used in the specification and claims are to be understood as being modified in all instances by the term "about". Accordingly, unless indicated to the contrary, the numerical values set forth in the following specification and claims may vary depending upon the desired properties sought to be obtained by the present invention. At the very least, and not as an attempt to limit the application of the doctrine of equivalents to the scope of the claims, each numerical value should at least be construed in light of the number of reported significant digits and by applying ordinary rounding techniques. Moreover, all ranges disclosed herein are to be understood to encompass the beginning and ending range values and any and all subranges subsumed therein. For example, a stated range of "1 to 10" should be considered to include any and all subranges between (and inclusive of) the minimum value of 1 and the maximum value of 10; that is, all subranges beginning with a minimum value of 1 or more and ending with a maximum value of 10 or less, e.g., 1.0 to 3.8, 6.6 to 9.7 and 5.5 to 10.
- As used herein, the terms "applied on/over", "formed on/over", "deposited on/over", or "provided on/over" mean formed, deposited, overlay or provided on but not necessarily in contact with the surface. For example, a coating layer "formed over" a substrate does not preclude the presence of one or more other coating layers or films of the same or different composition located between the formed coating layer and the substrate. For instance, the substrate can include a conventional coating such as those known in the art for coating substrates, such as glass or ceramic.
- As used herein, the term "running a coater" refers to the operation of a coater in a manner that results in a coating layer(s) being deposited on a substrate.
- The method of the present invention comprises running a single zone of an MSVD coater in at least two different modes to deposit a layer(s) of coating on a substrate. The present invention therefore defines a method of coating a substrate in a single zone of a MSVD coater wherein the zone includes at least two bays, comprising: running a first bay of a zone including a first target in metal mode to deposit a metal layer on the substrate, wherein the first target is selected from gold, copper, silver, titanium, zirconium, hafnium, yttrium and mixtures and alloys thereof; and running a second bay of a zone including a second target in transition or oxide mode to deposit an oxide layer on the substrate, wherein the second target is selected from titanium, silicon, zinc, aluminum, and combinations thereof, and wherein running the second bay includes pumping oxygen as a reactive gas into the zone.
- According to the present invention, conventional MSVD processes and equipment are utilized as is well known in the art. Suitable MSVD processes are described in the following references:
U.S. Patent Nos. 4,379,040 ;4,861,669 ; and4,900,633 . - One further example of such a process is disclosed in
US5298048 , furthermoreUS6045896 discloses heat-treatable glazings. Typically, the zone is a vacuum chamber equipped with various pumps to evacuate the chamber and to introduce one or more gases into the chamber as is well known in the art. The zone is isolated from other zones in the MSVD coater by narrow tunnels and/or pumps. The zone contains at least two targets, generally three. Each target is housed in a bay which has its own gas feed. Although the targets have separate gas feeds, all of the gas fed into the zone is pumped out from one location. - The targets utilized in the present invention are typical targets as are well known in the art for an MSVD process. A non-limiting example of a suitable target is a rotary target commercially available from AIRCO Coating Technology under the trademark "C-MAG". Non-limiting examples of suitable targets include those made of gold, copper, silver, zirconium, hafnium, aluminum, and yttrium as well as combinations of the aforementioned metals and alloys thereof. The previously mentioned targets are generally used to sputter deposit as a metal layer; hence, they are generally sputtered in metal mode. Other non-limiting examples of suitable targets include those made of titanium, silicon, tin, zinc, aluminum, combinations thereof, etc. The previously mentioned targets are generally used to sputter deposit as an oxide layer; hence, they are generally sputtered in either transition mode or oxide mode.
- In a non-limiting embodiment of the invention, a target can comprise from 5 weight percent to 95 weight percent aluminum and 5 weight percent to 95 weight percent silicon, for example, 10 weight percent to 90 weight percent aluminum and 90 weight percent to 10 weight percent silicon, or 15 weight percent to 90 weight percent aluminum and 85 weight percent to 10 weight percent silicon, or 50 weight percent to 75 weight percent aluminum and 50 weight percent to 25 weight percent silicon. Specifically, the target can comprise 60 weight percent silicon and 40 weight percent aluminum; or 25 weight percent silicon and 75 weight percent aluminum; or 90 weight percent silicon and 10 weight percent aluminum.
- The targets in the zone need to be chosen effectively to carry out the present invention. More particularly, the targets that can be placed in a single zone to carry out the present invention depend on the coating to be deposited, the Gibbs Free Energy of formation (ΔG) of the target oxides in the zone, and the deposition rates of the respective targets. ΔG is energy which is, or which can be, available to do useful work.
- ΔG can be defined in the following manner. ΔG = ΔH - TΔS where H is the enthalpy, S is the entropy, and T is the absolute temperature. As used herein, the terms enthalpy, entropy, and absolute temperature are defined as is well known the art.
- In a non-limiting embodiment of the invention, the ΔG of the target(s) oxides being run in transition mode or oxide mode is equal to or less than -160 kcal/mole O2, for example -165 kcal/mole O2. When ΔG is equal to or less than -160 kcal/mole O2, the target absorbs all of the reactive gas and there is none left to bleed through to other targets in the zone. Numerical values for the ΔG for many oxides can be found in Free Energy of Formation of Binary Compound, by Thomas Reed, MIT Press, ISBN 0 262 18051 0.
- In a non-limiting embodiment of the invention where the target(s) being run in transition mode or oxide mode is not equal to or less than -160 kcal/mole O2, the difference in ΔG between the target(s) being run in transition mode or oxide mode and the target(s) being run in metal mode should be at least 60 kcal/mole O2, for example, at least 75 kcal/mole O2, or at least 100 kcal/mole O2. The bigger difference in ΔG between the target(s) being run in transition mode or oxide mode and the target(s) being run in metal mode, the better the invention will operate because the chances of any bleed through is minimized. Also, the closer the ΔG of the target(s) being run in transition mode or oxide mode is to zero, the more bleed through is likely to occur because the target's affinity to react with reactive gas in its bay is not as high.
- In some cases, the amount of bleed through (and hence the difference in ΔG between the target(s) being run in transition mode or oxide mode and the target(s) being run in metal mode) is not as important as it is in others. The required difference in ΔG between the target(s) being run in transition mode or oxide mode and the target(s) being run in metal mode depends on the coating layers that are being deposited. For example, if a bay including a titanium target is being sputtered in metal mode to deposit a layer of titanium, but the layer of titanium is being deposited to eventually convert to titania, the bleed through from a bay being run in oxide mode or metal mode is less critical to the formed coating configuration. The titanium is being deposited so that it may be oxidized during subsequent processing.
- In another non-limiting embodiment of the present invention where a bay(s) is being run in metal mode to deposit a metal layer and the metal layer is desired in the final coating, only a minimal amount of bleed through from a bay(s) in the zone being run in transition mode or oxide mode can be tolerated. Otherwise, a compound like an oxide layer rather than a metal layer will be deposited. Table 1 below contains ΔG values for some common target materials, reference being made to the fact that tin, platinum and their oxides are not part of the present invention.
Table 1. ΔG Values Material ΔG [kcal/mole O2] Cu2O -70 Pt -32 SnO2 -130 TiO -242 TiO2 -216 ZnO -160 Ag2O -12 Al2O3 -258 SiO2 -216 ZrO2 -258 - As is well known in the art, the deposition rate of a particular target can be adjusted to account for a given amount of bleed through. For example, if a bay being run in transition mode or oxide mode is bleeding through oxygen, the deposition rate of the target can be slowed by reducing the power to the target. By reducing the deposition rate of the target, the reactions between the target and the reactive gas can be increased. The more reactions occurring between the reactive gas and the target, the less bleed through from the bay.
- The method of the present invention can be used on various substrates. Examples of suitable substrates include, but are not limited to, metal substrates, such as but not limited to steel, galvanized steel, stainless steel, and aluminum; ceramic substrates; tile substrates; glass substrates; or mixtures or combinations of any of the above. For example, the substrate can be conventional untinted soda-lime-silica-glass, i.e., "clear glass", or can be tinted or otherwise colored glass, borosilicate glass, leaded glass, tempered, untempered, annealed, or heat-strengthened glass. The glass can be of any type, such as conventional float glass or flat glass, and can be of any composition having any optical properties, e.g., any value of visible radiation transmission, ultraviolet radiation transmission, infrared radiation transmission, and/or total solar energy transmission. Types of glass suitable for the practice of the invention are described, for example but not to be considered as limiting, in
U.S. Patent Nos. 4,746,347 ;4,792,536 ;5,240,886 ;5,385,872 ; and5,393,593 . - In non-limiting embodiments where glass is the substrate, the substrate can be any thickness. Generally, the substrate is thicker for architectural applications than for automotive applications. In a non-limiting embodiment for an architectural application, the substrate can be glass having a thickness ranging from 1 mm to 20 mm, for example, 1 mm to 10 mm, or 2 mm to 6 mm. In a non-limiting embodiment for an automotive application, the substrate can be at least one glass ply in a laminated automotive windshield or sidelight. In automotive applications, the glass typically is up to 5.0 mm thick, for example, up to 3.0 mm thick, or up to 2.5 mm thick, or up to 2.1 mm thick.
- The glass substrate can be manufactured using conventional float processes, e.g., as described in
U.S. Patent Nos. 3,083,551 ;3,220,816 ; and3,843,346 . - According to the present invention, the following steps are undertaken to accomplish the method of the present invention. First, the proper gaseous atmosphere is created in each zone by continuously pumping one or more inert gases and/or one or more reactive gases into the bays in the zone and pumping the gas out at one location in the zone. As is well known in the art, the proper gaseous atmosphere depends on the composition of the coating layer(s) that is being deposited.
- Second, after the proper gaseous atmosphere is established, movement of the substrate through the zone is initiated and the magnetrons are energized. Molecules of the inert gas begin a cascade ionization process and form a plasma cloud of ions and electrons between the target and the substrate. The core of the plasma cloud has equal amounts of positive and negative charges. The positively charged ions at the plasma cloud edge, driven by an electric field, leave the plasma cloud and move toward the target surface and bombard the target material. The bombardment causes the target to disintegrate atom-by-atom in the direction of the substrate and ultimately deposit on the substrate.
- When the target is being sputtered in transition mode or oxide mode, the molecules of the reactive gas in the bay react with the sputtered atoms of the target material as they travel through the plasma cloud and impinge on the substrate. The end result is a deposited layer comprising a reacted compound, e.g., an oxide or a nitride of a metal, on the substrate. When the target is being sputtered in metal mode, the plasma cloud impinges on the target material to cause a metal layer to be deposited on the substrate.
- As the substrate passes through different zones in the multi-zone coater, various coating layers are sequentially deposited on the substrate. The coating compositions produced via MSVD processes are uniform, very adherent and resistant to abrasion, peeling and cracking.
- In a non-limiting embodiment of the invention, during the sputtering process, a portion of the substrate is only exposed to one target at a time. This embodiment allows discreet layers of coating to be deposited from a single target.
- In another non-limiting embodiment of the invention, during the sputtering process, a portion of the substrate is exposed to more than one target of different materials at a given time. This embodiment enables a layer of coating to be deposited that is a mixture of materials from more than one target (e.g., a gradient coating layer).
- For example, a gradient layer comprised of two materials, a first material and a second material, as described below can be formed. The gradient layer can be deposited in such a manner that the concentration of the first material is greatest near the bottom of the coating layer and the concentration of the second material changes, e.g., gradually increases, as the distance from the bottom of the coating layer increases. The region of coating furthest from the bottom of the coating layer has the greatest concentration of the second material.
- A substrate coated according to the present invention can receive additional layer of coating and can be heated. In a non-limiting embodiment of the invention, the coated substrate is heated, for example, to oxidize or further oxidize a metal within the coating stack.
- Additional layers such as a heat absorbing material like carbon can be applied on the coated substrate. Such a coating layer is beneficial if the coated substrate will need to be heated rapidly. Because all of the carbon can be consumed during the heating process, a final coated substrate can be made that does not include the carbon layer.
- In a non-limiting embodiment of the present invention, a zone in a MSVD multi-zone coater has at least one bay run in metal mode and at least one bay run in either transition mode or oxide mode. The bay that will be run in metal mode comprises a target comprising silver as is well known in the art. A gaseous stream comprised of an inert gas, like argon, is fed into the bay containing the silver target. The silver target is sputtered to deposit a layer of silver on the substrate. The sputtering is carried out using conventional power levels and under standard conditions as is well known in the art.
- The bay that will be run in either transition mode or oxide mode comprises a target comprising a mixture of aluminum and silicon as is well known in the art. Two gaseous streams are fed into the bay containing the aluminum/silicon target. One stream comprises an inert gas, like argon, and the other stream comprises a reactive gas, like oxygen. The aluminum/silicon target is sputtered to deposit a layer of a mixture of alumina and silica on the silver layer. The amount of reactive gas in the bay being run in transition mode or oxide mode is established such that the reactive gas does not bleed through to the bay being run in metal mode.
- If the bay is being run in transition mode, the gaseous environment in the bay is maintained to have very low levels of oxygen to keep the deposition rate of the target as high as possible. The minimum amount of oxygen necessary to deposit the target of aluminum and silicon as an oxide is fed into the bay. The amount of oxygen in the bay is adjusted every few milliseconds by means of a feedback system like a plasma emission monitoring (PEM) which is well known in the art. The amount of reactive gas in the bay is very important for several reasons. If too much reactive gas is present in a bay, reactions occur on the target surface (referred to as "target poisoning" in the art) and not in the sputtered plasma, causing the deposition rate to decrease from a transition mode rate to an oxide mode rate. If too little reactive gas is present in the bay, a sub-stoichiometric compound, such as a sub-oxide, and not the desired compound will be deposited on the substrate.
- In the non-limiting embodiment discussed above, the thickness of the deposited silver layer can range from 50 Å to 300 Å, for example, from 60 Å to 200 Å, or from 70 Å to 150 Å. The thickness of the deposited alumina/silica layer can range from 40 Å to 400 Å, for example, 100 Å to 350 Å, or 150 Å to 250 Å.
- Optionally, a bay containing a target comprising a second metal that is different from the other metal in the zone, i.e. silver in this embodiment, can be located in a third bay between the two bays discussed above. Suitable second metals for the target include gold, copper, silver, titanium, zirconium, hafnium, yttrium and mixtures and alloys thereof.
- In a non-limiting embodiment of the invention, a target comprising titanium as is well known in the art is located in a bay between the silver target and the aluminum/silicon target in the non-limiting embodiment discussed above. The titanium target can be used to react with any reactive gas bleeding through from the bay being run in transition mode or oxide mode comprising aluminum and silicon so that no reactive gas reaches the bay housing the metal being run in metal mode.
- In another non-limiting embodiment of the present invention, at least one bay in a zone is run in oxide mode and another bay in the zone is run in transition mode. The bay that will be run in oxide mode contains a target comprising a mixture of aluminum and silicon as is well known in the art. Two gaseous streams are fed into the bay. One stream comprises an inert gas, like argon, and the other stream comprises a reactive gas, like oxygen. The aluminum/silicon target is sputtered to deposit a layer of alumina/silica on the substrate. The sputtering is carried out using conventional power levels and under standard conditions as is well known in the art.
- The bay that will be run in transition mode contains a target comprising titanium as is well known in the art. Two gaseous streams are fed into the bay containing the titanium target. One stream comprises an inert gas, like argon, and the other stream comprises a reactive gas like, oxygen. The titanium target is sputtered to deposit a titanium-containing layer on the layer of alumina/silica. The gaseous environment in the bay is maintained to have very low levels of oxygen to keep the deposition rate of the target as high as possible. The minimum amount of oxygen necessary to deposit the target as an oxide is fed into the bay. The amount of oxygen in the bay is adjusted every few milliseconds by means of a feedback system like a plasma emission monitoring (PEM) which is well known in the art.
- The thickness of the deposited alumina/silica layer can range from 40 Å to 400 Å, for example, from 100 Å to 350 A, or from 150 Å to 250 Å. The thickness of the deposited titanium-containing layer can range from 10 Å to 150 Å, for example, 20 Å to 110 Å, or 60 Å to 90 Å.
- One of the unique aspects of the described embodiment is that it sputters a material that isn't an oxide at the time of deposition but can be converted to an oxide by heating or other means. Specifically, the deposited titanium can be converted to titania by heating.
- It will be readily appreciated by those skilled in the art that modifications may be made to the invention without departing from the concepts disclosed in the foregoing description. Such modifications are to be considered as included within the scope of the invention. Accordingly, the particular embodiments described in detail hereinabove are illustrative only and are not limiting as to the scope of the invention, which is to be given the full breadth of the appended claims and any and all equivalents thereof.
Claims (14)
- A method of coating a substrate in a single zone of a MSVD coater wherein the zone includes at least two bays, comprising:a. running a first bay of a zone including a first target in metal mode to deposit a metal layer on the substrate, wherein the first target is selected from gold, copper, silver, titanium, zirconium, hafnium, yttrium and mixtures and alloys thereof; andb. running a second bay of a zone including a second target in transition or oxide mode to deposit an oxide layer on the substrate, wherein the second target is selected from titanium, silicon, zinc, aluminum, and combinations thereof, and wherein running the second bay includes pumping oxygen as a reactive gas into the zone.
- The method according to claim 1 wherein the first target comprises silver.
- The method according to claim 1 or 2 wherein the second target comprises a mixture of aluminum and silicon.
- The method according to claim 3 wherein the second target comprises 60 weight percent silicon and 40 weight percent aluminum.
- The method according to claim 3 wherein the second target comprises 25 weight percent silicon and 75 weight percent aluminum.
- The method according to claim 3 wherein the second target comprises 90 weight percent silicon and 10 weight percent aluminum.
- The method according to any of the preceding claims further comprising running a bay containing a third target comprising a second metal that is different from the first metal in metal mode, the third target is located in a third bay between the first bay and the second bay.
- The method according to claim 7 wherein the second metal is selected from gold, copper, silver, titanium, zirconium, hafnium, yttrium and mixtures and alloys thereof.
- The method according to claim 8 wherein the second metal is titanium.
- The method according to any of the preceding claims wherein the coated substrate is glass.
- The method according to claim 3 wherein the first target comprises silver in metal mode and the second target comprises a mixture of aluminum and silicon in transition mode.
- The method according to claim 11 used to deposit a layer of alumina/silica over a layer of silver.
- The method according to claim 3 wherein the first target comprises titanium in metal mode and the second target comprises a mixture of aluminum and silicon in transition mode.
- The method according to claim 13 further comprising heating the substrate after it leaves the zone.
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PL05795589T PL1753891T3 (en) | 2004-05-06 | 2005-05-06 | Msvd coating process |
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US10/841,986 US8500965B2 (en) | 2004-05-06 | 2004-05-06 | MSVD coating process |
PCT/US2005/016133 WO2006007062A2 (en) | 2004-05-06 | 2005-05-06 | Msvd coating process |
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EP1753891A2 EP1753891A2 (en) | 2007-02-21 |
EP1753891B1 true EP1753891B1 (en) | 2021-09-01 |
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US (1) | US8500965B2 (en) |
EP (1) | EP1753891B1 (en) |
CN (1) | CN1950534B (en) |
PL (1) | PL1753891T3 (en) |
RU (1) | RU2341587C2 (en) |
WO (1) | WO2006007062A2 (en) |
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2005
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- 2005-05-06 EP EP05795589.0A patent/EP1753891B1/en active Active
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CN1950534A (en) | 2007-04-18 |
US8500965B2 (en) | 2013-08-06 |
WO2006007062A2 (en) | 2006-01-19 |
EP1753891A2 (en) | 2007-02-21 |
RU2341587C2 (en) | 2008-12-20 |
RU2006143063A (en) | 2008-06-20 |
PL1753891T3 (en) | 2022-01-31 |
CN1950534B (en) | 2011-12-07 |
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